Silver halide color photography utilizing magenta-dye-forming couplers



United States Patent 3,419 391 SILVER HALIDE COLOR lHOTOGRAPHY UTILIZ- ING MAGENTA-DYE-FORMING COUPLERS David V. Young, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed May 24, 1965, Ser. No. 458,455 13 Claims. (Cl. 9656.5)

ABSTRACT OF THE DISCLOSURE 4-pyrazolin-5-one magenta dye-forming couplers having an aryloxy group substituted on the active methylene group in the coupling position of the coupler have good coupling reactivity and other valuable properties and are advantageously used in color photography as couplers incorporated in photographic elements or in color developer solutions.

This invention relates to color photography and more particularly to new and improved magenta dye-forming coupler compounds for use in image-forming systems and processes utilizing such couplers for the formation of images. In a more specific aspect, my invention relates to two-equivalent coupler compounds for forming magenta dye images in color photography.

The formation of color photographic images by the imagewise coupling of oxidized aromatic primary amino developing agents with color-forming or coupling compounds to form indoaniline, indophenol, and azomethine dyes is well known. In these processes, the subtractive process of color formation is ordinarily used and the image dyes customarily formed are cyan, magenta, and yellow, the colors that are complementary to the primary colors, red, green, and blue, respectively. Usually phenol or naphthol couplers are used to form the cyan dye image; pyrazolone of cyanoacetyl derivative couplers are used to form the magenta dye image; and acylacetamide couplers are used to form the yellow dye image.

In these color photographic systems, the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that, during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development. Diifusable couplers are used in color developer solutions. Nondiffusing couplers are incorporated in photographic emulsion layers. When the dye image formed is to be used in situ, couplers are selected which form nondiffusing dyes. For image transfer color processes, couplers are used which will produce diffusible dyes capable of being mordanted or fixed in the receiving sheet.

Most of the couplers which have been used in the various color photographic systems described above are four-equivalent couplers, that is, they require reduction of 4 mols of silver halide for the formation of 1 mol of dye. Certain of the prior art couplers are two-equivalent couplers, i.e., they require reduction of only 2 mols of silver halide for the formation of 1 mol of dye. However, some of the prior art two-equivalent couplers exhibit serious disadvantages such as low reactivity, formation of an unacceptably high level of color fog, and other undesirable side reactions.

It is an object of my invention to provide new and improved class of two-equivalent -pyrazolone couplers capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent, said couplers having an aryloxy group substituted on the carbon in the 4 position of the heterocyclic ring.

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It is a second object to provide my novel couplers which have a materially reduced tendency to produce unwanted color density in the non-image areas.

It is another object of this invention to provide novel two-equivalent couplers With greatly reduced propensity to unwanted side reactions and hence higher dye yield.

It is a further object of this invention to provide new and improved two-equivalent magenta couplers which have greatly increased reactivity, thereby obviating prolonged or forced development.

It is another object of my invention to provide im proved color photographic image-forming layers containing my novel couplers dispersed in a colloidal filmforming binder.

It is another object of my invention to provide a simple, economical, and reproducible process for preparing my couplers in high yield.

It is a further object to provide photographic silver halide-gelatin emulsion layers containing my new couplers for use in color photography.

It is another object of my invention to provide improved photographic magenta dye images by the use of my novel couplers.

These and other objects will appear from the following description of my invention.

These and other objects are accomplished by the use in color photography of the two-equivalent couplers of my invention wherein one of the hydrogen atoms of the active methylene group in the pyrazolone nucleus has been replaced with an aryloxy radical. By aryloxy I mean unsubstituted aryloxy or substituted aryloxy, e.g., oxarloxy or arylenedioxy.

The couplers of my invention may be represented to advantage by the formula:

wherein n represents an integer of from 1 to 2, R represents any of the 4-pyrazoyl-5-one groups that are found in any of the S-pyrazolone couplers that are known in the art, and R represents an aryl or an arylene group. Although the effectiveness of my couplers as two-equivalent couplers is not dependent on the specific composition of R and R it will be understood that these radicals may contain various substituent groups and that the character and the degree of substitution may be modified according to such requirements, e.g., spectral absorbtivity, reactivity, solubility, and diffusibility, as may be imposed by the photographic system in which the coupler is to be used. My couplers have at least one 4-pyrazolyl-5-one group with an active methylene group in the 4-position.

Accordingly, the couplers of my invention may be further represented by the following formula:

wherein R represents an alkyl group including a straight or branched chain alkyl group of from about 1 to about 30 carbon atoms, preferably from 1 to 22 carbon atoms (e.g., methyl, isopropyl, tertiary butyl, hexyl, dodecyl, docosyl, etc.), a monocyclic alkyl group (e.g., cyclohexyl, etc.), a bicyclic alkyl group, such as, a terpenyl group especially a norbornyl group (e.g., norbornyl, 7,7-dialkylnorbornyl, 2-phenyl 7,7 dialkylnorbornyl, 2-pentadecyl- 7,7-dialkylnorbornyl, etc.), a substituted alkyl group in which any of the described alkyl groups contain any of the substituted groups used in couplers, such as, a halogen, the nitro group, the hydroxyl group, the carboxyl group,

an amino group (e.g., amino, N-alkylamino, N,N-dialkylamino, N-arylamino, N-alkyl, N-arylamino, etc.), a carboxy ester (e.g., carbomethoxy, carboethoxy, carbophenoxy, etc.), the sulfo group, a sulfo ester (cg, methoxysulfonyl, butoxysulfonyl, phenoxysulfonyl, etc.), an amide group (e.g., acetamido, butyramido, [a-(ZA-di-t-a-mylphenoxy)acetamidol benzamido, a-( 3 pentadecylphenoxy)butyramido, a-(4-t-butylphenoxy)propionamido, 3,5- dicarboxybenzamido, ethylsulfonamido, phenylsulfonamido, etc.), a carbamyl group (e.g., N-methylcarbamyl, N-phenylcarbarnyl,etc.), a sulfamyl group (e.g., N-propylsulfamyl, N-tolylsulfamyl, etc.), an alkoxy group (e.g., methoxy, butoxy, etc.), an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy, etc.), including the substituents defined for substituted alkyl groups above, R also represents ene alkyl, etc.), such that the said R groups can contain any of the substituent groups as defined previously for such groups in R My novel couplers are characterized by having an aryloxy group on the coupling position of the coupler which gives them good coupling reactivity and other valuable properties. These couplers are particularly characterized by the low levels of unwanted color fog and low printout and yellowing they produce in photographic elements that use the said couplers for image formation. Excellent coupling reactivity is obtained with couplers of my invention when incorporated in emulsion layers without the use of high-boiling coupler solvents. When high-boiling solvents are used to disperse these couplers, high dye yield and low color fog are attained over a wide range of couplera heterocyclic group having from 5 to 6 atoms in the ring 10 to-solvent ratios. When the diiiusible couplers of my inincluding nitrogen, sulfur, oxygen, etc., as the heterovention are used in color developing solution, excellent atoms and including heterocyclic groups, such as, furanyl, reactivity and good dye yield are achieved. benzothiazolyl, oxazolyl, imidazolyl, quinolinyl, etc., a Included among my novel couplers are the following substituted heterocyclic group in which any of the hetcro- 2O typical examples which are used to illustrate but not limit cyclic groups are substituted by any of the substituents my invention. described above as being on the substituted alkyl groups, Coupler 1.-l-phenyl-3-methyl 4 (4-methylsulfonyl- R also represents a carbamyl group (e.g., alkylcarbamyl, phenoxy)-5-pyrazolone arylcarbamyl, heterocyclic carbamyl, etc.), and R also represents a thiocarbamyl group (e.g., alkylthiocarbamyl, arylthiocarbamyl and heterocyclicthiocarbamyl), in which the alkyl, aryl and heterocyclic groups in the said carbamyl CCH and thiocarbamyl groups may be substituted with any of g the substituents described for R when it represents an alkyl, aryl or heterocyclic group itself; R represents hydrogen, an alkyl group, an aryl group and a heterocyclic group (unsubstituted or substituted) as described pre- Coupler viously for R R also represents a carhoxy ester (e.g., yl'N'octadecylsulfamyl)phenoxy] 5 'Pyrazolone Sodlum carbopropoxy, carbobutoxy, carbophenoxy, etc.), a subsalt stituted oxy group (e.g., methoxy, ethoxy, decyloxy, z phenoxy, tolyloxy, etc.), a substituted thio group (e.g., NaOsSN I ethylthio, propylthio, phenylthio, tolylthio, etc.), an amino group (e.g., amino, N-alkylamino, N-arylamino, N,N- I dialkylamino, N-alkyl, N-arylarnino, etc.), an amido o 0 group (e.g., acetamido, a-(2,4-di-t-amylphenoxy)acet- 40 l amido, a-butylphenoxypropionamido, a-(3-pentadecyl-4- A sulfophenoxyacetamido)benzamido, etc.), a carbamyl group (e.g., carbamyl, N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-niethyl-N phenylcarbamyl, 3 pentadecylphenylcarbamyl, etc.), sulfamyl, a ureido group (e.g., an SOzN N-arylureido group, an N-alkylureido group, etc.), a thioureido group (e.g., an N-alkylthioureido group, an N-arylthioureido group, etc.) a guanidino group (e.g., guanidino, N-arylguanidino, N-alkylguanidino, etc.), such Coupler 3.l-(2,4,6-trich1orophenyl)-3-{3-[a-(2,4-dithat the alkyl and aryl groups in R may contain subt-amylphenoxy)acetamido]benzamido} 4 (4-nitrophestituent groups as defined previously for such groups in noxy)-S-pyrazolone N=ONHCO Q I o1 N I Q NI-ICOCHzO- C ,Hn-t

oC-H 01 ll I (I) CsIIn-b l NO:

R 11 represents an integer of from 1 to 2; R represents Coupler 4.-1 phenyl 3 methyl 4-(2,4-dinitrophean aryl group, such that when n represents the integer 1, 0 noxy)-5-pyrazolone R represents a monovalent aryl group (eg, phenyl, alkyl- Coupler 5.1-phenyl-3-anilino-4-phenoxy-S-pyrazolone sulfonylphenyl, arylsulfonylphenyl, N -alkylsulfamyl- Coupler 6.1 phenyl 3 octadecylamino 4 (4 phenyl, N,N-dialkylsulfamyl-phenyl, N-arylsulfamylphennitrophenoxy -5-pyrazolone yl, N-alkyl-N-arylsulfamylphenyl, sulfamylphenyl, nitro- Coupler 7.1 phenyl 3 octadecylamino 4 (4 phenyl, acetamidophenyl, halophenyl, naphthyl, pyridyl, acetamidophenoxy)-5-pyrazolone methoxyphenyl, octadecoxyphenyl, hydroxyphenyl, sulfo- Coupler 8.l {4 [on (3-pentadecylphenoxy)butyrphenylazophenyl, carboxyphenyl, sulfophenyl, etc.), and amidoJphenyl} 3 ethoxy 4 (4 nitrophenoxy) 5- when n represents the integer 2, R represents a divalent pyrazolone aryl group (e.g., phenylene, naphthylene, diphenylene, Coupler 9.-l phenyl-3-pentadecyl-4-(2-chloro-4-sulpyridylene, quinolylene, dipheuylene sulfone, w,wphenylfamylphenoxy) -5-pyrazolone Coupler 10.-1,4-(stearamidophenyl)-3-ethoxy-4-(2,4- dinitrophenoxy)-5-pyrazolone Coupler ll.l-[4-(4-t-butylphenoxy)phenyl]3-[or-(4- t-butylphenoxy)propionamido] 4 hexafiuorophenoxy)- S-pyrazolone Coupler 12.l-[4-(4-t-butylphenoxy)phenyl]-3-[a-(4- t butylphenoxy)propionarnido] 4 (l naphthyloxy)- S-pyrazolone Coupler 13.-1-[4-(4-t-butylphenoxy)phenyl1-3-[or-(4- t butylphenoxy)propionarnido] 4 (4 pyridyloxy)-5- pyrazolone Coupler 14.1 [4-t-butylphenoxy)phenyl]-3-[tx-(4-tbutylphenoxy)propionamido] 4 (4 chlorophenoxy) 5-pyrazolone Coupler 15.1-methyl-3-(3,5-dicarboxybenzamido)-4 (4-nitro-3-pentadecylphenoxy)-5-pyrazolone Coupler 16.-1 phenyl 3 octadecylcarbamyl 4 [4 (N methyl N phenylsulfamyl)phenoxy] 5 pyrazolone Coupler 17.-1 (2,4,6 trichlorophenyl) 3 {3 [a (2,4 di t amylphenoxy)acetamido]benzamido} 4- [4-hydroxyphenylsulfonyl phenoxy] -5-pryazolone Coupler 18.1 phenyl 3 (3,5 dicarboxyanilino) 4- 4-octadecyloxyphenoxy -5 -pyrazolone Coupler 19.1 phenyl 3 [N (11,;8 dicarboxyethyl)ureido] 4 (4 nitro 3 pentadecylphenoxy) 5 pyrazolone Coupler 20.1-(2,4-dichloro-6methoxyphenyl)-3-{3- [or (3 pentadecyl 4 sulfophenoXy)acetamido]benzamido}-4- (4nitrophenoxy) -5-pyrazolone Coupler 2l.1-(2,4 dichloro-6-methoxyphenyl)-3-{3- [a (3 pentadecyl 4 sulfophenoxy)acetarnido]benzamido}-4-(4-acetamidophenoxy)-5-pyrazolone Coupler 22.1 phenyl-3-{2-ch1oro-4-{3-[m-(3-pentadecylphenoxy) acetamido]benzamido}anilino} 4 [4- (4-sulfophenylazo phenoxy] -5-pyrazolone Coupler 23.1-(2,4,6,-tricholorophenyl)-3-{5-[a-(2,4- di t amylphenoxy) acetamido] 2 methoxyanilino} 4- [4- N,N-diethylsulfamyl phenoxy] -5 -pyrazolone Coupler 24.1 {4 [a (3-t-butylphenoxy)tctradecanamido] 2,6 dichlorophenyl} 3 (2,4 dichloroani1ino)-4-(4-rnethylsulfonylphenoxy)-5-pyrazolone Coupler 25.1 (2,4,6 trichlorophenyl) 3 {2 [a (3 pentadecylphenoxy)acetamido)anilino} 4 (4 nitrophenoxy)-5-pyra2olone Coupler 26.l (2,4,6 trichlorophenyl) 3 {2 [oz- (3 pentadecylphenoxy)acetamido]anilino} 4 (4-acetamidophenoxy)-5-pyrazolone Coupler 27.1 (2,4,6 trichlorophenyl) 3 (4 nitroanilino -4- 4-sulfarnylphenoxy) -5-pyrazolone Coupler 2 8.1-(2,4,6-trichiorophenyl)-3-{2achloro-4 [or (2,4 di t amylphenoxy)butyramidolanilino} 4- (4-sulfophenoxy)-5-pyrazolone Coupler 29.1 phenyl 3 anilino 4 (4 carboxyphenoxy)-5-pyrazolone Coupler 30.1 phenyl 3 pentadecyl 4(4 hydroxyphenoXy)-5-pyra2olone Coupler 3 l.l-phenyl-3-{3- [a- 3-pentadecylphenoxy acetamido1benzamido} 4 (2,5 diiodo 4 hydroxyphenoXy)-5-pyrazolone Coupler 32.4,4' bis[l (4 cyanophenyl) 3 (5 butyramido 2 chloroanilino) 4 pyrazol 5 onyloxy1- diphenylsulfone Coupler 33.1 (4 sulfophenyl) 3 methyl 4 (4 sulfophenoxy)-5-pyrazolone disodium salt Coupler 34,1,4 bis[1 phenyl 3 (4 hexanamidoanilino 4-p-yrazol-5-onyloxy] benzene Coupler 3 5.l- 2-benzothjazolyl -4- (4-nitrophenoxy 5-pyrazolone Coupler 36.1-carbamyl-4-(4 nitrophenoxy)-5-pyrazoione Coupler 37.1 thiocarbamyl-4-(2,4-dinitrophenoxy)- S-pyrazolone Coupler 3S.-1 phenyl 3 phenylthio 4 (3 nitrophenoxy -5-pyraz0l0ne Coupler 39.1 phenyl 3 methylthio 4 (3 nitrophenoxy)-5-pyrazolor,e

Coupler 40.1 phenyl 3 guanidino 4 (2,4 dinitrophenoxy)-5-pyrazolone Coupler 41.1 phenyl 3 carbamyl 4 (2,4 dinitrophenoxy)-S-pyrazolone The couplers of my invention are distinguished by their high reactivity and the very low density of unwanted color fog they produce during color development. The aryloxy group provides a means of attaching other substituents to my couplers such as, for example, preformed dyes useful in color correction, dye transfer processes and the like. Additional ballasting groups can conveniently be introduced via the aryloxy group; these ballasting groups are then eliminated during the coupling reaction with oxidized color developer which forms the image dyes.

The ditfusible couplers of my invention, such as couplers 1, 4, 5, 27, 29 and 35 through 41 are used to advantage in color developer solutions used to color develop light-sensitive elements use-d for color photography which do not contain the co1or-forrning coupler. Any of the well known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g., diethyl-p-phenylenediamine hydrochloride, monomethylp-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2 amino S-diethylaminotoluene hydrochloride, 2 amino-5-(N-ethyl-N-laurylarnino)toluene, N-ethyl-N- B-rnethanesulfonarnidoethyl -3methyl-4- aminoaniline, 4- [N -ethyl-N- ;8-hydroxyethyl) amino 1 aniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with my couplers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in vicous developer compositions such as carboxyrnethyl cellulose, carboxyethyl cellulose, gelatin, etc. The following is a typical developer solution given to illustrate but not limit my invention.

g. 2-amino-5-dicthylaminotoluene HCl 2.

Sodium sulfite (anhydrous) 2.0 Sodium carbonate monohydrate 20.0 Potassium bromide 1.0

Coupler 2.0

Water to 1000.0 ml.

Coupler 33 is a diffusible coupler which forms a diffusible dye on coupling with oxidized color developer, and may be used to advantage in color developer solutions as a competing coupler.

The other coupler examples used to illustrate my invention are nondiifusing and are used to advantage in photographic emulsion layers. Couplers such as 20, 21, 22 and 28, illustrate those that are incorporated as Fischer-type couplers. The other nondiffusing couplers, e.g., 3, 6-14, 16, 17, 23-26, 3032, and 34, are incorporated in emulsion layers by methods such as are described by Mannes et al., US. Patent 2,304,939, issued Dec. 15, 1942, Ielley et al., US. Patent 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents are used to dissolve the coupler, and by methods described in Vittum et al., US. Patent 2,801,170, and Fierke et al., US. Patent 2,801,171, both issued July 30, 1957, and Julian U.S. Patent 2,949,360, issued Aug. 16, 1960, in which low-boiling or Water-soluble organic solvents are used with or in place of the high-boiling solvent. The use of such coupler dispersions permits thinner emulsion layers. These thinner layers are very desirable because they cause less light scattering, consequently, they produce sharper images.

The nondiltusing couplers, 2, 15, 18 and 19, contain free acid groups (i.e., carboxy and sulfo) so that the dyes formed by these couplers are rendered diffusing. This valuable property enables these couplers to be used to advantage in image-transfer processes and as incorporated, diffusible-dye-forming competing couplers in conventional color films.

Coupler 22 contains a preformed dye attached to the coupler on the aryloxy group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film. This coupler can be used as a yellow-colored coupler for the purpose of correcting for the unwanted blue absorption of magneta image dyes, i.e., that formed from the coupler itself as well as that formed from other magenta couplers. Generally, such a coupler as this would be used in combination with another image-forming magneta coupler in the same layer.

My couplers are used to advantage in the color development of photographic silver halide layers of the developing-out type in the silver halide layer or in a contiguous layer. The silver halide may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Usually the silver halide is in a hydrophilic colloid emulsion.

Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in US. Patent 2,286,215, a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, as described in US. Patent 2,327,808, a water-soluble ethanolamine cellulose acetate as described in US. Patent 2,322,085, a polyacrylamide having a combined acrylamide content of 3060% and a specific viscosity of 0.25-1.5 on an imidized polyacrylamide of like acrylamide content and viscosity as described in US. Patent 2,541,474, zein as described in US. Patent 2,563,79l, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in US. Patent 2,768,154, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in US. Patent 2,808,331, or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in US. Patent 2,852,382.

The light-sensitive layers(s) used in the photographic element of my invention can be chemically or optically sensitized by any of the accepted procedures.

The couplers of my invention may also be used to advantage in image-forming layers, either alone or with image-forming compounds other than silver halide, such as ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without binders such as gelatin, polyvinyl alcohol, etc.

Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a red-sensitive layer, a green-sensitive layer, and blue-sensitive layer either with or without a bleachable yellow-colored layer, such as a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the bluesensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet. The reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine 8 derivatives of vinyl methyl ketone such as described in Minsk, US. Patent 2,882,156, granted Apr. 14, 1959.

My invention is further illustrated by the following typical examples.

Example 1 Samples of a single layer gelatin silver bromoiodide coating were exposed (i.e., for second on a 1B intensity scale sensitometer). These strips were then processed to color positives by the following process; all process temperatures were 68.

4-amino 3 methyl-N-ethyl-N-B-(methanesulfonamido)ethyl aniline sesquisulfate hydrate g 5.0 Sodium carbonate monohydrate g 50.0 Sodium bromide g 0.2 Water to pH to 10.75 liter 1 1 The couplers used in the above-mentioned developer formula were couplers l, 4, 5, 27 and 29, respectively.

Good magneta dye images were formed in each of the respective strips.

EXAMPLE 2 Single layer gelatin silver bromoiodide coatings were prepared containing couplers 3, 6, 8, ll, 13, 17, 23 and 24, respectively. Each of these couplers were dispersed in said coatings in the form of a finely-dispersed solution of the coupler in coupler solvent, di-n-butylphthalate. These coatings contained 10 parts of gelatin, 5 parts of silver, 2 parts of coupler, and 1 part of coupler solvent. Samples of the abovernentioned coatings were given second exposure on a 1B intensity scale and processed in a conventional manner to color negatives, respectively, using the following developer solution.

Sodium sulfite (anhydrous) g 2.0 2-amino-5-diethylaminotoluene HCl g 2.0 Sodium carbonate monohydrate g 20.0 Potassium bromide g 2.0 Water to pH to 10.86 liter 1.0

Each of the processed strips contained high quality magenta dye images.

EXAMPLE 3 Single layer gelatin silver bromoiodide coatings containing couplers 2, 15, 18 and 19, respectively, were prepared. These coatings were similar to those described in Example 2 above except that the couplers were dispersed directly in the gelatin. Samples of these coatings were exposed as described in Example 2 above, and processed by developing each of them for 5 minutes at F. in contact with a receiving sheet containing a mordaut which had been presoaked in the following developer solution.

Sodium carbonate monohydrate g 22.0 Ascorbic acid g 0.24 Potassium bromide g 0.8 Sodium sulfite (anhydrous) g 2.0 4-amino N ethyl-N-fl-hydroxyethyl-aniline sulfate g 11.0 Water to make pH adjusted to 12.5 using 20% sodium hydroxide solution liter 1.0

After the development period, samples of the film were removed from the mordant receiving sheet, in which sheets were contained the respective transferred and mordanted magenta dye images.

Similarly, other couplers of my invention are used to advantage in color photography as illustrated previously with representative couplers. Further, the couplers of my invention are valuable as magenta image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film. Such other couplers are, for example, yellow image-forming couplers containing a methylene or substituted methylene group having two carbonyl groups directly attached thereto, and cyan couplers such as naphthols and phenols.

In general, my couplers are the product of the reaction of an ethyl a-aryloxyacetoacetate or an ethyl ot-aryloxy-B-methylthio-B-anilinoacrylate with an aromatic hydrazine. The intermediate ester is prepared by reacting an aromatic hydroxy compound with an ethyl a-halo-fiketoester in the presence of an alkaline condensing agent.

Alternatively, my couplers may be prepared by reacting the sodium salt of 4-hydroxy-5-pyrazolone with fluoro benzenes, which benzenes are activated by having an electron withdrawing substituent attached to the benzene ring, e.g., nitro, sulfo, etc.

The following preparations will illustrate the various methods which were used to prepare my magenta-forming two-equivalent couplers.

Preparation of coupler 1.l-phenyl-3-methyl-4-(4- methylsulfonylphenoxy)-5-pyrazolone The intermediate ethyl 2-(4-methylsulfonylphenoxy)- acetoacetate was prepared as follows. To a hot solution of 17 g. of 4-methylsulfonylphenol and g. of triethylamine in 250 ml. of acetonitrile was added 16 g. of ethyl- 2-chloroacetoacetate. The reaction mixture was refluxed for 6 /2 hours, after which time it was left overnight at room temperature. The triethylamine hydrochloride which precipitated from the mixture was separated and the resultant solution was concentrated to a volume of ml. Additional triethylamine hydrochloride which separated was again removed. To the concentrated solution was then added 300 ml. of cold Water, whereupon a white solid precipitated, was collected and air dried. This solid was recrystallized once from a mixture of 150 ml. of ethyl alcohol and 300 ml. of water, and a second time from 100 ml. of methyl alcohol to yield 8.5 g. of product having a melting point of l08109 C.

A mixture of 2 g. of ethyl 2-(4-methylsulfonylphenoxy)acetoacetate (prepared above) and 1 g. of phenylhydrazine hydrochloride in 25 ml. of absolute ethyl alcohol was refluxed for 1 hour. The resulting clear solution was allowed to cool to room temperature, whereupon a solid separated. This solid was recrystallized from 100 ml. of ethyl alcohol to yield the product, coupler 1.

Preparation of coupler 2.1-(4-sulfophenyl)-3-methyl- 4 [4 (N methyl-N-octadecylsulfamyl)phenoxyJ-S- pyrazolone sodium salt A mixture of 5.7 g. of ethyl a-acetyl-a-[4-(N-methyl- N-octadecylsulfamyl)phenoxy]acetate, 1.9 g. of p-hydrazinobenzene sulfonic acid, and 0.82 g. of sodium acetate in 50 ml. of glacial acetic acid was refluxed for 1 hour,

after which time an additional 0.82 g. of sodium acetate was added to the hot solution. The reaction mixture was refluxed for an additional 30 minutes and allowed to cool to room temperature overnight, during which time a solid separated. This solid was collected and air dried. To the filtrate was added 150 ml. of ethyl ether, and the solid which separated was also collected. The total solids were combined and recrystallized from 20 ml. of dimethylformamide to yield the product, coupler 2.

Preparation of coupler 3.-1-(2,4,6-trichlorophenyl)-3- {3 [on (2,4 di t amylphenoxy)acetamido]benzamido}-4- (4-nitrophenoxy) -5 -pyrazo1one Intermediate No. 1.1-(2,4,6-trichlorophenyl)-3-{3-[a- (2,4 di t amylphenoxy)acetamido]benZamido}-4-hydroxyimino-S-pyrazolone: To a solution of 67 g. of 1-(2, 4,6 trichlorophenyl) 3-{3-[a-(2,4-di-t-amylphenoxy)- acetamido]benzamido}-5-pyrazolone in 500 ml. of glacial acetic acid was added 12 g. of isopentyl nitrite with stirring at room temperature. The reaction mixture was stirred for approximately 20 minutes, after which time an orange solid began to precipitate. The mixture was stirred for a total of 1 hour, and the solid which separated was collected and recrystallized from ethyl alcohol to yield 56 g. of the product, M.P. -148 C.

Intermediate N0. 2.1-(2,4,6-trichlorophenyl)-3-{3- [oz-(2,4 di t amylphenoxy)a-cetarnido]benzarnido}-4- amino-S-pyrazolone tin (SnCl salt: To a solution of 5 g. of Intermediate No. 1 above in ml. of 3A ethyl alcohol was added a mixture of 7 g. of anhydrous stannous chloride in 20 ml. of concentrated hydrochloric acid. The resultant solution was warmed on a steam bath for 10 minutes, during which time it changed from a bright orange color to a very pale yellow. The mixture was cooled to room temperature and poured into 200 ml. of cold water, whereupon a white solid separated, was collected and air dried to yield the product.

Intermediate No. 3.1-(2,4,6 trichlorophenyl)-3-{3- [IX-(2,4 di t amylphenoxy)acetamido]benzamido}-4, 4-dihydroxy-5-pyrazolone: To a solution of 2.5 g. of Intermediate 2 above in 25 ml. of 3A ethyl alcohol was added a hot solution of 20 g. of ferric chloride hexahydrate (FeCl -6H O) and 5 ml. of concentrated hydrochloric acid in 100 ml. of 3A ethyl alcohol. The resultant solution was heated on a steam bath for 10 minutes, after which time it was cooled to room temperature and poured into 200 ml. of cold water, whereupon a white solid separated, was collected and dried to yield 1.8 g. of the product.

Intermediate No. 4.1-(2,4,6-trichlorophenyl)-3-{3- [c:-(2,4 di t amylphenoxy)acetamido]benzamido}-4- hydroxy-S-py-razolone: A solution of 1.2 g. of Intermediate No. 3 above in 50 ml. of absolute ethyl alcohol was hydrogenated on the low pressure Parr hydrogenation apparatus using 10% palladium on charcoal as the catalyst for 20 minutes at room temperature. The reduction solution was then filtered to remove the catalyst, concentrated in vacuo to yield the product, which was used without further purification.

Coupler 3, named above: To a solution of Intermediate No. 4 above and an equivalent amount of anhydrous sodium methylate in 10 m1. of dimethyl formamide (i.e., which had been saturated with nitrogen) was added an equivalent amount of 4-nitrofiuorobenzene. The resultant solution was headed on a steam bath for 2 /2 hours, after which time was added 10 ml. of 5% acetic acid, whereupon a solid precipitated, was collected, and recrystallized from methyl alcohol to yield the product.

Preparation of coupler 4.1-phenyl-3-rnethy1-4- (2,4-d initrophenoxy -5pyrazolone To a solution of 1 g. of 1-phenyl-3-methyl-4-hydroxy- S-pyrazolone and 0.5 g. of sodium methylate in 5 ml. of dimethyl formamide (i.e., which had been saturated with nitrogen) was added 1 g. of 2,4-dinitrofluorobenzene with stirring at room temperature. The reaction mixture was stirred at room temperature for 30 minutes (i.e., cooling in an ice bath was required), after which time the solution was acidified with dilute acetic acid, whereupon a solid precipitated, was collected and dried to yield the product.

Preparation of coupler 5.-1-phenyl-3-anilino-4 'phenoxy-5-pyrazolone Intermediate No. 1.Ethy1 a-phenoxyacetoacetate: To

TABLE A Coupler Intermediate Fluorobenzene Coupler N 4 1-phenyl-3-oetadecylamino-4-hydroxy-S-pyrazolone 4n1trofluorobenzene.

3 1-t4-[a-(3-pentadecylphenoxy)-butyramido1phenyl}-3- Do.

ethoxy-i-hydroxy-Es-pyrazolone.

1-( t-stearamidophenyl)-3-ethoxy-4-hydroxy-5-pyrazolone 2,4-dinitrofluorobenzene.

11 1-[4-(4i-t-butylphenoxy)phenyl1-3-[a-(4t-butylphenoxy)- Hexafluorobenzene.

propionarnido]-4hydroxy-5-pyrazolone.

15 1-methyl-3-(3,S-dicarbomethoxybenzamido)-4-hydroxy-5- 4-nitro-3-pentadeey1fluorobenzene.

pyrazolone (The ester was then hydrolyzed to the free acid, cplr. 15, using alkaline hydrolysis).

19 l-phenyl-3-[N-(a,B-diearbethoxyethyl)ureido]-4-hydroxyethoxyethyl)ureido1-4-hydroxy-5-pyrazolone (The ester was then hydrolyzed to the free acid, cplr. 19, using alkaline hydrolysis).

20 1-(2,4-dichloro-dmethoxyphenyl)-3-i3-[a-(3-pentadeeyH- 4-nitrofluorobenzene.

suliophenoxy)aeetamide1-benzamido} -4hydroxy-5- pyrazolone.

1(2,4,6trichlorophenyl)3-t2-[a-(3-pentadeeylphenoxy) Do.

aeetamidohnilino} -4hydroxy-5pyrazolone.

28 1-(2,4,6trichlor0phenyl)-3-l2-chloro-4-[a-(2,4-di-t-amyl- 4-fluorobenzene sulionic acid.

phenoxy)butyramidolanilino} -4-hydroxy-5-pyrazolone.

29 1-phenyl-3-anilmo-thydroxy-fi-pyrazolone i-fluorobenzoie acid.

33 1-(4-s11liophenyl)-3-methyl-4 hydr0xy-5-pyrazolone (The -fluorobenzene sulronic acid.

free acid was converted to the disodium salt with sodium acetat e. 22 1-phenyl-3-{2-chl0r0-4-l3-[cx-(3-pentadeeylphenoxy) acet- 4-( i-fluoropheuylazo benzene sulfuric acid.

amido]-b enz amide} anilino} -4-hydr0xy-5-pyraz olone.

a slurry of 23 g. of sodium phenolate in 1 liter of dry Couplers 35 through 41 are prepared to advantage by anhydrous benzene heated to reflux was added 165 g. of D the procedure used to prepare coupler 3 using the respecethyl oc-ChlOI'OfiCBlOElCfitatC with stirring over a period of tive intermediates given in the following Table A.

TABLE A Coupler N 0. Coupler Intermediate Fluorobenzene 35 1-(2-benz0thiazolyl)4-hydroxy-5-pyrazolone 4-nitrofiuor0benzene. 36 1-carbamyl-4-hydroxy-5-pyrazolone 0- 37 l-thlocarbamyli-hydroxy-5-pyraz0lone. 2,4-dinitrofiuoroben- Z9119. 38 1-phenyl3-phenylthio-4'hydroxy-S-pyrazoloue. 3-nitrofluorobenzene. 39 1-pl1enyl-3-methylthio-i-hydroxy-5-pyrazol0ne Do. 40 1-pl1enyl-3-guanidino4-hydroxy-5-pyrazolone. 2,4-dinitroflu0r0ben- Z8118. 41 l-phenyl-(icarhamyl-tlrydroxy-S-pyrazolone. D0.

30 minutes. The reaction mixture was stirred and re- Couplers 7, 21 and 26 were each prepared by the catafluxed for 4 hours, after which time it was washed wlth lytic reduction (i.e., using palladium on charcoal as the 2X 500 ml. of water, dried over magnesium sulfate, catalyst) of couplers 6, 20 and 25, respectively. These filtered, and concentrated in vacuo to yield the product. amino intermediates were then each acylated using acetyl Intermediate No. 2.Ethyl a-phenoxyx-isothiocyanochloride to yield couplers 7, 21 and 26, respectively. cetoacetate sodium salt: To arefluxing solution of sodium r Couplers 9, 12, 13, 14, 16, 17, 30 and 31 were each etholate (i.e., prepared by reacting 23 g. of metallic so- 05 prepared in accordance with the procedure given for dium in 300 ml. of methanol) in 300 ml. of absolute ethyl coupler l; couplers 18, 23, 24 and 27 were each prealcohol was added Intermediate No. 1 above. To the repared in accordance with the procedure given for cousultant solution was then added 135 g. of phenyhsothiopler 5 using the respective intermediates given in Table cyanate over a period of 5 minutes with stirring. This B below. solution was refluxed for an additional 5 minutes after the addition had been completed, after which time it was TABLE B cooled to 20 C. The product was isolated and used as h Coupler Ester Intermediate Hydrazine Suc N0. Intermediate Intermediate No. 3.--Ethyl u-phenoxyfl-methylth1o-fi- 9 E H m 04 mi d] h Ph m at C 01' '5 011311111 0 8110K en aanilmoacrylate. To a solution of Intermediate No. 2 6' ocmdecanoam Y y above was added, at room temperature with stirring, 147 12 Ditighyl-aill-niaphggylgxy]pgxilfacetate reg-Bu iugeose 0 0 31 8 oxypyraz- CHOXY g. of iodomethane. The solution was allowed to stir at 010m; hydrolyzedto the acid; com ghenymydw room temperature for 15 minutes and then was refluxed vertedto ga e itlzlid iazide; Curtius1rearzine,

rangernen 0 6 -am1nopyrazo one; for an additlonal 15 minutes. The product was isolated acylate the aminewith the appropriate d d as ch atlzid enhllorige, ti-t-)butylphenoxy-a-methi yaceye one. Coupler 5, named abme. To the refluxing solution of 13 Diethyl a l4 pyridyloxyloxaloacetate DO. Intermediate No. 3 above was added 108 g. of phenyl- (lRingglllosed to tl11 3-:;)rbethoxypyraz- 0 one, en (IS in O. hydrazine. The resultant solution was refluxed for 6 hours, 14 Diethy1 a [4 ammo]phenoxyoxaloacetate D0 after which time it was cooled to room temperature, and (Ring closed to 3-carbethoxypyrazolone; held at room temperature for 2 days. A small amount of menus 111 3- TABLE B Coupler Ester Intermediate Hydrazine No. Intermediate 16 Diethyl-a-[4-N-methyl-N-phenylsuliona- Phenylhydramido]phenoxyoxaloacetate (Ring closed to 3-carbethoxypyrazolone; then as in No. 12.). 17 Diethyl-a-[4-(i-hydroxyphenyl)-sulfony1- 2,4,6-trichlorozine.

phenoxyloxaloacetate (Treated as in phenylhydra- N0. 12.). zine.

18 Ethyl-a-l t-octadecyloxyl-phenoxy-B-meth- Phenylhydraylthio-B-[3,5-dicarboxy1anilinozine. acrylate.

23 Ethyl-a-[4-N,N-diethylsulfe.myl]phe- 2,4,6-tr1chloronoxy-B-methylthiofl-[2-methoxy-5-nitro1- phenylhydraanillnoacrylate (Ring closure followed zine. by hydrogenation of nitro function to amino; acylate amine with appropriate acid chloride, 2,4-di-t-amylphenoxyacetyl chloride.)

24 Ethyl-a-[kmethylsulfonyl]-phenoxy-B- 2,6-dichloro-4- methylthio B-2,4-dichloroanilinonitrophenylacrylate. hydrazine. The

intermediate nitro compound was catalytically reduced and the resultant amino compound was acylated with a-(4-t-bl1l3ylphenoxy) tetradecanoyl chloride to yield coupler 24.

27 Ethyl-a-[4-sulfamyl]phenoxy-B-methyl- 2,4,6-trichll'0- thio-fi-i-nitroanilinoacrylate. phenylhydra- Zinc.

30, Ethyl-2-[ i-hydroxy]phenoxy-3-oxooctadec- Phenylhydreanoate. zine.

31 Diethyl-ar-[2,5-diiodo-4-hydroxy1phenoxy- Do.

oxaloacetate (Ring closed to the 3-carbethoxypyrazolone; hydrolyzed to the acid; converted to acid chloride; converted to acid azide; Curtius rearrangement to the firaminopyrazolone: 3- amino function acylated with the appropriate acid chloride, 3-[a-(3-pentadecylphenoxy)-acetamido1benzoyl chloride).

32 4,4-Sullonyldiphenol bisla-carbethoxy- 4-cyanophenyl- B-methylthiofi-(2-chloro-5-nitro)anilinohydrazine. vinylether] (Chemically reduce the nitro function to amine and acylate amine with butyryl chloride).

34 Hydroquinone hisIB-carbethoxy-B-meth- PhenylhytlraylthioBp-n'itroanilino vinylether] zine.

(Catalytically hydrogenete the nitro function to amine and acylate amine with hexanoyl choride.).

The two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplers by having an aryloxy group substituted on the coupling position of the coupler molecule. My couplers are characterized by not producing color fog, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity. Further, my novel couplers exhibit very low printout and yellowing when they are incorporated into photographic coatings relative to that exhibited by many of the prior art magenta couplers. Printout is the percent change in transmission (i.e., to a light source having a predominant wavelength of 420 me) that is produced in an area of the processed strip having no exposure (i.e., D min. area) by 30 hours exposure to a Xenon arc lamp. Yellowing is the percent change in transmission (i.e., to a light source having a predominant wavelength of 420 m produced in an unexposed area of the processed strip (i.e., D min. area) by exposing the strip for 1 week to a temperature of 140 F. and 40% relative humidity.

These couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler to solvent ratios.

My couplers are not only valuable for the reasons cited, but because photographic emulsion layers color developed with them require only one-half the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondiflusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high-boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images. The couplers of my invention may be used in emulsion layers or in color developer solutions either alone or admixed with other couplers, either fouror two-equivalent couplers, competing couplers, and the like.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected Within the spirit and scope of the inventio as described hereinabove and as defined in the appended claims.

I claim:

1. An image-forming layer containing silver halide and a coupler which is capable of forming a nondifiusible dye on coupling with the oxidation product of an aromatic primary amino color developing agent, said coupler containing from one to two 4-pyrazolyl-5-one groups each having an active methylene group in the 4-position, said 4-pyrazolyl-5-one being directly joined through said active methylene group to an aryloxy group such that when the said coupler contains one 4-pyrazolyl-5-one group the said aryloxy group is a monovalent group selected from the class consisting of a phenoxy group, a naphthyloxy group, and a pyridyloxy group and when the said coupler contains two 4-pyrazolyl-5-one groups the said aryloxy group is a divalent group selected from the class consisting of a phenylenedioxy group, a naphthalenedioxy group, and the 4,4'-bisoxydiphenyl sulfone group.

2. An image-forming layer containing silver halide and a coupler which is capable of forming a nonditfusible dye on coupling with the oxidation product of an aromatic primary amino color developing agent, said coupler having the formula:

0 ll wherein R presents a group selected from the class consisting of an alkyl group, an aryl group, a heterocyclic group and a carbamyl group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxy ester group, a substituted oxy group, a substituted thio group, an amino group, an amido group, a ureido group and a guanidino group; n represents an integer of from 1 to 2; R represents a group selected from the class consisting of a phenyl group, a naphthyl group, and a pyridyl group when n represents the integer 1, and R represents a divalent group selected from the class consisting of a phenylene group, a naphthylene group and the diphenylene sulfone group when n represents the integer 2.

3. An image-forming layer containing silver halide and a coupler which is capable of forming a nondilfusible dye on coupling with the oxidation product of an aromatic primary amino color developing agent, said coupler having the formula:

wherein R2 represents a group selected from the class consisting of an alkyl group, a phenyl group, a heterocyclic group, and a carbamyl group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, a phenyl group, a heterocyclic group having from 5 to 6 atoms in the heterocyclic ring, a carboxy ester group, a substituted oxy group, a substituted thio group, an amino group, an amido group, a ureido group and a guanidino group; n represents an integer of from 1 to '2; R represents a group selected from the class consisting of a phenyl group, a naphthyl group, and a pyridyl group when n represents the integer 1, and R represents a divalent group selected from the class consisting of a phenylene group, a naphthylene group and the diphenylene sulfone group when n represents the integer 2.

4. An image-forming layer containing silver halide and a coupler which is capable of forming a nondiffusible dye on coupling with the oxidation product of an aromatic primary amino color developing agent, said coupler having the formula:

wherein R represents a group selected from the class consisting of lower alkyl, a phenyl group, a benzothiazolyl, carbamyl and thiocarbamyl; R represents a group selected from the class consisting of hydrogen, alkyl of from 1 to 15 carbon atoms, alkoxy of from 1 to 10 carbon atoms, a carbamyl group, a benzamido group, a propionamido group, ureido, an anilino group, alkylamino having from 1 to 18 carbon atoms, guanidino, phenylthio and methylthio; and R represents a divalent group selected from the class consisting of a phenylene group, a naphthylene group and the diphenylene sulfone group.

5. An image-forming layer containing silver halide and a coupler which is capable of forming a nondiffusible dye on coupling with the oxidation product of an aromatic primary amino color developing agent, said coupler having the formula:

wherein R represents a group selected from the class consisting of lower alkyl, a phenyl group, a benzothiazolyl, carbamyl and thiocarbamyl; R represents a group selected from the class consisting of hydrogen, alkyl of from 1 to 15 carbon atoms, alkoxy of from 1 to 10 carbon atoms, a carbamyl group, a benzamido group, a propionamido group, ureido, an anilino group, alkylamino having from 1 to 18 carbon atoms, guanidino, phenylthio and methylthio; and R represents a group selected from the class consisting of a phenyl group, a naphthyl group and a pyridyl group.

6. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing 1-(4-sulfophenyl)-3-methyl-4- [4-(N-methyl-N-octadecylsulfarnyl) phenoxyH-S pyrazolone sodium salt.

7. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing 1-(2,4,6-trichlorophenyl)-3-{3- [u-(lA-di-t-amylphenoxy)acetamido]benzamido} 4 (4- nitrophenoxy)-5-pyrazolone.

8. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing 1-{4-[u-(3-pentadecylphenoxy)- butyramido]phenyl}-3-ethoxy 4 (4-nitrophenoxy)-5-pyrazolone.

9. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing 1-[4-(4-t-butylphenoxy)phenyl]-3-[u-(4-t-butylphenoxy)propionamido] 4 (4-chlorophenoxy -5-pyrazolone.

10. A light-sensitive hydrophiliccolloid-silver halide emulsion layer containing 1-(2,4-dichloro-6-methoxyphenyl)-3-{3-[a-(3-pentadecyl 4 sulfo) phenoxy] benzamido}-4- (4-nitrophenoxy -5-pyrazolone.

11. An aqueous alkaline magenta color-forming devel- 1 6 oper solution comprising an aromatic primary amino color developing agent and a difiusible coupler capable of reacting with said developing agent in oxidized form to form a nondiffusible dye, said coupler having the formula:

wherein R represents a group selected from the class consisting of an alkyl group, a phenyl group, a heterocyclic group, and a carbamyl group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, a phenyl group, a heterocyclic group having from 5 to 6 atoms in the heterocyclic ring, a carboxy ester group, a substituted oxy group, a substituted thio group, an amino group, an amide group, a ureido group and a guanidino group; R represents a group selected from the class consisting of a phenyl group, a naphthyl group and a pyridyl group.

12. An aqueous alkaline magenta color-forming developer solution comprising an aromatic primary amino color developing agent and a ditfusible coupler capable of reacting with said developing agent in oxidized form to form a nondiffusible dye, said coupler having the formula:

wherein R represents a group selected from the class consisting of a phenyl group, a benzothiazolyl group, carbamyl, and thiocarbamyl; R represents a group selected from the class consisting of hydrogen, lower alkyl, an anilino group, phenylthio, lower alkylthio, guanidino and carbamyl; and R represents a group selected from the class consisting of a phenoxy group and a pyridyloxy group.

13. A process for forming a magenta dye image in an image-forming silver halide layer comprising the step of contacting the said layer with an aqueous developer solution comprising an alkali and an aromatic primary amino developing agent in the presence of a coupler which is capable of forming a nonditfusible magenta dye on coupling with the oxidation product of an aromatic primary amino developing agent, said coupler containing from one to two 4-pyrazolyl-5-one groups each having an active methylene group in the 4-position, said 4-pyrazolyl-5-one being directly joined through said active methylene group to an aryloxy group such that when the said coupler contains one 4-pyrazolyl-5-one group, the said aryloxy group is a monovalent group selected from the class consisting of a phenoxy group, a naphthyloxy group, and a pyridyloxy group and when the said coupler contains two 4-pyrazolyl-S-one groups the said aryloxy group is a divalent group selected from the class consisting of a phenylenedioxy group, a naphthalenedioxy group, and the 4,4'-bisoxydiphenyl sulfone group.

References Cited UNITED STATES PATENTS 1/1966 Whitmore et al. 96100 1/1966 Barr et al. 9610O 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 1 39 Dated December 31 I 968 Inventor(s) David V- YOullg It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 15, line 52, the term, "phenoxyl", should read --phenoxy.

SEALED D51; 2 3 1959 (SEAL) Attest:

EdwardM. Fletcher, Ir. LLIAM E- SOHUYLER, JR, Altestmg Officer comissioner of Patents 

